Chiral Assembly and Recognition of Seven Copper (II) Coordination Polymers from Tartaric Acid Derivative Ligands.

A pair of enantiomeric ligands, (2R,3R)-dibenzyl-2,3-bis(isonicotinoyloxy)succinate ((R,R)-L) and (2S,3S)-dibenzyl-2,3-bis(isonicotinoyloxy)succinate ((S,S)-L), are designed and synthesized. Seven copper (II) coordination polymers {[Cu((R,R)-L)Br2 (THF)] ⋅ CH3 CN} n (1 a) and {[Cu((S,S)-L)Br2 (THF)] ⋅ CH3 CN}n (1 b), {[Cu((R,R)-L)Cl2 (THF)] ⋅ CH3 CN}n (2 a) and {[Cu((S,S)-L)Cl2 (THF)] ⋅ CH3 CN}n (2 b), {[Cu((R,R)-L)(NO3 )2 (CH3 CN)]}n (3 a) and {[Cu((S,S)-L)(NO3 )2 (CH3 CN)]}n (3 b), {[Cu((R,R)-L)2 (CH3 CN)2 ](ClO4 )2 ⋅ 3CH3 CN}n (4) were obtained through the assemblies with CuBr2 , CuCl2 ⋅ 2H2 O, Cu(NO3 )2 ⋅ 3H2 O, Cu(ClO4 )2 ⋅ 6H2 O, respectively. Single-crystal X-ray diffraction and circular dichroism analysis demonstrate that 1 a-3 a, 1 b-3 b have a mono chiral one-dimensional (1D) chain-like spiral structure, while 4 have 1D chain-like structure whose metal centers have chiral propeller coordination environment. Ligand structure, anions and solvent systems have a regulatory effect on the formation of chiral helical structure. Further investigation has proved that 1 a can be used as circular dichroism spectrum probe for monitoring L-/D-cysteine and L-/D-penicillamine configuration and concentration in aqueous media based on ligand interchange mechanism.

Dinuclear HgII tetracarbene complex-triggered aggregation-induced emission for rapid and selective sensing of Hg2+ and organomercury species.

Rapid, reliable and highly selective detection of mercury species, including Hg2+ ions and organomercury, is of significant importance for environmental protection and human health. Herein, a new fluorescent dye 1,1,2,2-tetrakis[4-(3-methyl-1H-benzimidazol-1-yl)phenyl ethylene tetraiodide (Tmbipe) with aggregation-induced emission (AIE) potential was prepared and characterized. The presence of four positively charged methylated benzimidazole groups endows Tmbipe with excellent water solubility and almost undetectable background fluorescence. However, it can coordinate with two Hg2+ ions or two organomercury molecules (e.g. methylmercury and phenylmercury) to form a planar dinuclear HgII tetracarbene complex, which can then self-aggregate to turn on AIE fluorescence. Such a fluorescence turn-on process can be completed in 3 min. In addition, synergic rigidification of the tetraphenylethylene-bridged Tmbipe molecule by mercury-mediated chelate ring formation and subsequent aggregation results in obviously higher fluorescence enhancement than that given by the single aggregation-induced one. Low background, high fluorescence enhancement and rapid response time make Tmbipe a good fluorescent probe for reliable, sensitive and highly selective quantitation of both inorganic and organic mercury species. This probe was also demonstrated to work well for identification of mercury species accumulation in living cells.

Comparison of caries and sealants between Shanghai native and migrant 12-year-old students from 2013 to 2015 / 上海交通大学学报（医学版）

Objective·To compare the caries prevalence, unmet restoration needs and sealant prevalence between Shanghai 12-year-old native and migrant students from 2013 to 2015. Methods·From 2013 to 2015, a random cluster sample of 12-year-old native and migrant students was selected from each district in Shanghai. World Health Organization (WHO) indices were used to assess decayed-missing-filled teeth of permanent dentition (DMFT). The prevalence of caries and sealants, caries filling rate, unmet dental restoration needs and the value of DMFT were analyzed using the Mann-Whitney U test and chi-squared test. Results·A total of 2500 students were examined from 2013 to 2015, among which 36.8％ were migrants. There was no significant difference in caries prevalence and DMFT value between native and migrant students from 2013 to 2015. Sealant prevalence of migrants was significantly lower than that of natives in 2013 (0.8％ vs 6.6％) and 2015 (3.0％ vs 9.9％). Unmet restoration needs of migrants were significantly higher than those of natives in 2015 (60.5％ vs 46.4％). Conclusion·There was no significant difference in caries prevalence between 12-year-old native and migrant students in Shanghai from 2013 to 2015. But there were lower sealants and higher unmet restoration needs in 12-year-old migrant students than their native counterparts, even though free public dental health services were available to both groups.

A new cationic porphyrin derivative (TMPipEOPP) with large side arm substituents: a highly selective G-quadruplex optical probe.

The discovery of uncommon DNA structures and speculation about their potential functions in genes has brought attention to specific DNA structure recognition. G-quadruplexes are four-stranded nucleic acid structures formed by G-rich DNA (or RNA) sequences. G-rich sequences with a high potential to form G-quadruplexes have been found in many important genomic regions. Porphyrin derivatives with cationic side arm substituents are important G-quadruplex-binding ligands. For example, 5,10,15,20-Tetrakis(N-methylpyridinium-4-yl)-21H,23H-porphyrin (TMPyP4), interacts strongly with G-quadruplexes, but has poor selectivity for G-quadruplex versus duplex DNA. To increase the G-quadruplex recognition specificity, a new cationic porphyrin derivative, 5,10,15,20-tetra-{4-[2-(1-methyl-1-piperidinyl)ethoxy]phenyl} porphyrin (TMPipEOPP), with large side arm substituents was synthesized, and the interactions between TMPipEOPP and different DNA structures were compared. The results show that G-quadruplexes cause large changes in the UV-Vis absorption and fluorescence spectra of TMPipEOPP, but duplex and single-stranded DNAs do not, indicating that TMPipEOPP can be developed as a highly specific optical probe for discriminating G-quadruplex from duplex and single-stranded DNA. Visual discrimination is also possible. Job plot and Scatchard analysis suggest that a complicated binding interaction occurs between TMPipEOPP and G-quadruplexes. At a low [G-quadruplex]/[TMPipEOPP] ratio, one G-quadruplex binds two TMPipEOPP molecules by end-stacking and outside binding modes. At a high [G-quadruplex]/[TMPipEOPP] ratio, two G-quadruplexes bind to one TMPipEOPP molecule in a sandwich-like end-stacking mode.

Oxidative DNA cleavage by Schiff base tetraazamacrocyclic oxamido nickel(II) complexes.

Nickel is considered a weak carcinogen. Some researches have shown that bound proteins or synthetic ligands may increase the toxic effect of nickel ions. A systematic study of ligand effects on the interaction between nickel complexes and DNA is necessary. Here, we compared the interactions between DNA and six closely related Schiff base tetraazamacrocyclic oxamido nickel(II) complexes NiL(1-3a,1-3b). The structure of one of the six complexes, NiL(3b) has been characterized by single crystal X-ray analysis. All of the complexes can cleave plasmid DNA under physiological conditions in the presence of H(2)O(2). NiL(3b) shows the highest DNA cleavage activity. It can convert supercoiled DNA to nicked DNA then linear DNA in a sequential manner as the complex concentration or reaction time is increased. The cleavage reaction is a typical pseudo-first-order consecutive reaction with the rate constants of 3.27+/-0.14h(-1) (k(1)) and 0.0966+/-0.0042h(-1) (k(2)), respectively, when a complex concentration of 0.6mM is used. The cleavage mechanism between the complex and plasmid DNA is likely to involve hydroxyl radicals as reactive oxygen species. Circular dichronism (CD), fluorescence spectroscopy and gel electrophoresis indicate that the complexes bind to DNA by partial intercalative and groove binding modes, but these binding interactions are not the dominant factor in determining the DNA cleavage abilities of the complexes.